Heterocyclic sulphonamido azo compounds



the nomenclature of Beilstein, "Handbuch der organischen Chemie, 4thed., receive the following names: 7

(l) (2-aminopyridinesulphonyl)-benzene- 4-azo-5 -2-hydroxy-benzoic acid.

Brown-yellow substance, melting point about Easily soluble in 2N NaOHwith orange-red color.

Easily soluble in 2N NazCOs with orange-yellow color.

Slight solubility in concentrated acids.

(2-aminothiazolsulphonyl) -benzene- 4-azo-5 -2-hydroxy-benzoic acid.

Orange-yellow substance,melts with decomposition at about 200 C. Easilysoluble in 2N NaOH and 2N NazCOs with deep red color. acids.

(i-methyl 2 aminothiazolsulphonyl) benzene- 4-azo-5-2-hydroxy-benzoicacid.

Brown-yellow substance, melts with decomposition at about 220 C. Easilysoluble in 2N NaOH (deep red) and 2N NazCOa (orange) Slight solubilityinconcentrated acids.

(2-aminopyridinesulphonyl) -benzene 4-azo-5 -6-hydroxy-3-methyl-2 cumaronic acid.

(Z-aminopyridinesulphonyl) -benzene- 4-azo-5- -3-methyl-2- hydroxybenzoic acid.

Orange-yellow substance, melting point about Easily soluble in 2N NaOHwith orange-red color.

Easily soluble in 2N NazCOa with orange color.

Slight solubility in concentrated acids.

(6) (2-aminopyridinesulphonyl)-benzene- 4-azo-5 -2-hydroxy-1,3-dicarboxybenzene.

Regarding the preparation of the new substances in question, it has beenfound, that it is possible to employ not only the method consisting indiazotisation of the amino group of the sulphamide component andcoupling with the hydroxy acid, but that also other methods known per sefor the preparing of azo compounds may be employed to advantage, e. g.condensation of nitroso compounds with amino compounds to form azocompounds, or oxydation of hydrazo' compounds to azo compounds, orcondensation of hydroxylamino compounds with nitroso compounds to azoxycompounds and reduction to azo compounds. It is also possible, using oneof the aforementioned methods, first to prepare an azo compound from anaromatic amino compound containing substituted groups which are easilytransformed into sulphamide groups, and a hydroxycarboxylic acid notcontaining nitrogen whether in a nucleary bond or as amino comders within general slight solubility in water andother usual solvents. Inalkaline solution they will generally form more readily soluble saltshaving Slight solubility in concentrated a stronger color. They melt orsinter under decomposition upon heating.

In the following some typical examples of preparing the new compoundsare given.

Example 1 -50 grams of a-(p-aminobenzene-sulphonamido-) pyridine aredissolved in a mixture of 50 cos. of concentrated hydrochloric acid and25 cos. of water and diazotized with a solution of 13.8 grams sodiumnitrite. In the meantime 28 grams of salicylic acid, 24 grams ofpotassium hydroxide and 12 grams of sodium carbonate are dissolved inwater. .The diazo suspension is added in portions to the alkalinesolution of salicylic acid and the alkalinity maintained at asufficiently high levelduring the whole reaction by means of addition offurther quantities of potassium hydroxide solution. After 2 days thereaction mixture is heated for /g hour at 50 C. After cooling the azocompound formed is precipitated by means of hydrochloric acid andfiltered off. (The compound "having the constitution numbered (1) above,may be prepared in this way.)

Example 2 50grams of a-(p-aminobenzene sulphonamido) -pyridine isdiazotized as in Example 1. The coupling is made with amixture of 30grams of ortho-cresotinic acid, 24 grams of potassium hydroxide and 12grams of sodium carbonate in water. For the restit is operated as statedin Example 1. (The compound having the constitution numbered (5) above,may be prepared in this way.) i

' Example 3 Example 4 A solution of 17 grams of 5-nitroso-salicylic acidin 100 'ccs. alcohol is added to a mixture of 25 grams u-(p-aminobenzenesulph0namido-)py- 'ridine and cos. of glacial acetic acid. The reactionmixture is carefully warmed, whereby a homogeneous solution is firstformed. The azo compound soon begins to crystallize and separate out. Byaddition of water the crystallization is promoted. The azo compound isfiltered off, washed and dried. (The compound numbered 1) above may beprepared in this manner.)

, Ea'amz le 5 A solution of 5.3 grams ofa-(p-nitrosobenzenesulphonamido-)pyridine in 25 cos. of alcohol is addedto a solution of 3.8 grams amino-salicylic acid in 10 cos. of glacialacetic acid. The mixture compound numbered (1) above do-)pyridine ispulverized and suspended in 125 bonate solution. 2 grams of ammoniumchloride are added and the mixture is energetically stirred whereupon 15grams of powdered zinc are gradually added in portions. The temperatureof the solution is kept below 20 C. by means of adding lumps of ice tothe same. After 30 minutes 17 grams of pulverized 5-nitroso-salicylicacid and after this 15 grams of a30% solution of sodium hydroxide areadded to the reaction mixture. The mixture is heated to 50 C. and isthen allowed to cool and stand over night. The azoxy compound is nowprecipitated by means of hydrochloric acid, filtered, washed and dried.

33.7 grams of this azoxy compound are added to a solution of 22.6 gramsof crystallized stan- The azoxy compound is thereby reduced to thecorresponding azo compound. After a few hours the mixture is dilutedwith water, the azo compound is filtered ofi, washed and dried. (Thecompound numbered (1) above may be prepared in this manner.)

Example 7 25 grams of a-(paminobenzene-sulfonamido-) pyridine aredissolved in a mixture of 25 cos. of concentrated hydrochloric acid and25 cos. of water and diazotized by means of a solution of 6.9 grams ofsodium nitrite. In the meantime 13.5 grams of anthranilic acid aredissolved in a mixture of 50 cos. of water and 50 cos. of glacial aceticacid. The diazo solution and the solution of anthranilic acid are nowmixed and to themixture are added 18 grains of crystallized sodiumacetate. The stirring is continued and it is tested from time to time ifthe coupling has been completed and no free diazo compound is present.When this is the case the reaction mixture is mixed with 100 cos. ofglacial acetic acid and 60 cos. of concentrated hydrochloric acid; Themixture is cooled and diazotized with a solution of 6.9 grams of sodiumnitrite. The stirring is continued for 30 minutes after which thesolution is heated on steam bath until the evolution of nitrogen hasceased, and then for another 30 minutes. The hydroxyazo compound maythen be precipitated with water and is treated as above. (This proceduremay be followed for preparing the compound constituted as shown under(1) above.)

Example 8 nous chloridein concentrated hydrochloric acid.

25 grams of a-(p-aminobenzene sulfonamldo.-)

pyridine is diazotized as described in Example 1. The diazo compound isadded to a solution of 19.2 grams of6-hydroxy-methyl-cumarone-carboxylic acid, 12 grams of potassiumhydroxide and 6 grams of sodium carbonate in water. After this theprocedure is as according to Example 1. (In this manner the compoundnumbered (4) above may be prepared.)

Example 9 v numbered (6) above may be prepared in this manner.)

We claim:

1. Azo'compounds having bactericidal properties and having'the generalformula;

wherein R represents a benzene hydroxy-carboxylic acid group free fromnuclear attached amino groups, Y represents an unsubstituted benzenegroup in which the sulfamide group is in para position to the azo groupand X represents a substituent. selected from a class consisting ofpyridiyl, thiazolyl and methyl-subsituted thiazolyl groups, in whichnitrogen is nucleobound directly in the ring, said X being linked to theamide nitrogen by a carbon atom.

2. A20 compounds having bactericidal properties and having the generalformula:

wherein R represents a benzene hydroxy-carboxylic acid group free fromnuclear-attached amino groups, Y represents'an unsubstituted benzenegroup in which the sulfamide group is in para positionto the azo groupand X represents a pyridyl group.

3. The azo compound of the formula:

HO HOOC N=( OSOz-NH which compound forms water soluble salts withalkalies.

4. The azo compound of the formula:

which compound forms water soluble salts with alkalies.

ERIC EMIL ANDERS ASKELF. NANNA SVARTZ. HARRY CARLO WILLSTAEDT.

